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,ing the splittingoperatio ing oil vapors were maintained at a temperathe latter were pumped UNITED. STATES PATENT ormon. j

GARLETON ELLIS, or MONTCLAIR, NEW JERSEY, ASSIGNOR TO ELLIS-FOSTER COMPANY, A CORPORATION on NEW JERSEY.

PROQESS OF MAKING DERIVATIVES 0F PETROLEUM-HYDROGARBONS.

No Drawing. Original application filed August 21, 1913, Serial No. 785,855.

filed September 19, 1916, Serial No. 121,010.

To all whom it may concern: 7

Be it known that I, CARLETON ELLIS, a citizen of the UnitedStates, and a resident of Montclair, in the county of Essex and State of New Jersey, have invented certain new and useful Improvements in Processes of Making Derivatives of Petroleum-Hydrocarbons, of which the following is a speci' fication.

This invention relates to'a process of making derivatives of gasolene and relates in particular to the treatment of gasolene like material obtainedthrough the heat decomposition of kerosene or heavier oil and which contain large amounts of unsaturated materials and in chlorinating such unsaturated products to form dichlor compounds or higher chlorinated bodies as the case may be and furthermore in converting such chlorinated bodies by contact-with alkali material into dechlorinated bodies of acter,

The unsaturated hydrocarbon material is preferably prepared by passing a saturated hydrocarbon such-as kerosenethrough a heatedtube, as for example, an iron pipe which is preferably heated to 425 or 480 C.

and in some cases maybe filled with fragments of contact material such as nickel plated fragments of iron of irregular shape.

' cases water maybe introduced Also in some with the kerosene or other raw 011 used and allowed to react with the hydrocarbons dur- The product obtained by such heat treatmentor other suitable heat treatment of a more or less similar ch'aracter may then be separated into its lighter and heavier parts by fractional condensation and if desired the fractions obtained in this or other manner are subjected to fractionaldistillation to obtain particularly certain relatively lowboilin fractions of an unsaturated character. Tor example kerosene of 42 passed through a tube of considerable length heated to such a temperature that. the escaptureof about 4655; (3., which required a temperature about the tube of approximately 630 C. The vapors were passed through an air condenser, then through a water con-' denser and finally the gases escaping from through heavy oil in order to remove some of the entrained Specification of Letters Patent.

' original kerosene.

sene with a certain amount proximatlng kerosene in boiling point. This a useful c'har- B., was

foregoing heat treatment has in its preferred Patented Oct. 7 1919. Divided and this application condensable material. product as drawn from about 43 B., or.only

The gravity of the the heated tube was 1 lighter than the of products lighter and heavier than keroof bodies ap material was distilled and the product collected below 150 C. ,was redistilled in an ordinary distilling apparatus equipped with a rectifying column tions were obtained.

and the following frac-- It consisted of a mixture Fractions Percentage Iodin Per cent.

. ficient to split off their chlorin in large measure forming different varieties of unsaturated bodies or other useful material.

'The dechlorination may take place with replacement of the chlorih by some other element or radical as for example by an acid radical to form an ester. Thus the chlorinated compounds formed by treatment with chlorin or by union with hydrochloric acid or in any other suitable way may be treated with sodium acetate or other salt of acetic acid toform amyl acetate and other esters according to the nature of the materials used. By employing the salts of other organic acids such as formate, benzoate, etc, similar corresponding esters can be secured. These same esters and other complex esters may be secured from thechlorination prod ucts obtained by direct chlorination.

The gasolene material obtained by the liquid the Chlorin-' by volume.! number.

chlorin in the cold r oo ' 785,855, filed troleum oil through a heated form an iodin number not less than 30 but preferably is higher and may be in excess of 100. As stated the products of higher iodin number absorb chlorin with avidity and dichlor compounds are formed when a single double bond is present while in the case of diolefins and the like the chlorination may progress further as desired.

This application is a division of Serial No. Aug. 21, 1913, entitled Motor fuel and process of making same.

What I claim is l 1. The process of making derivatives of hydrocarbons which comprises passing petroleum oil through a heated zone maintained at a decomposing temperature under such conditions as to form lighter products of unsaturated character, in combining these unsaturated products, after fractional distillation, with chlorin, in reacting on the chlorinated body with an alkali metal salt of an organic acid and in separating the ester formed from other products of reaction.

2. The process of making derivatives of hydrocarbons which comprises passing petroleum oil through a heated zone maintained at a decomposing temperature under such conditions as to form lighter products of unsaturated character, in reacting on these unsaturated products with a chlorinating agent, in reacting on the chlorinated body so formed, with an alkali metal salt of an organic acid and in separating the ester formed from other products of reaction.

3. The process of making derivatives of. hydrocarbons which comprises passing petube main tained at a decomposing temperature under such conditions as to form very light products of unsaturated character, in combining these unsaturated products with chlorin, in reacting on the chlorinated body with a salt of an organic acid and in separating the ester formed from other products of reaction.

1. The process of making derivatives of hydrocarbons which comprises passing petroleum oil through a heated zone maintained at'a decomposing temperature under such conditions as to form lighter products of unsaturated character, in combining these unsaturated products with chlorin, in reacting on the chlorinated body with a salt of acetic acid and in separating the ester formed from other products of reaction.

5. The process of making derivatives of hydrocarbons which comprises bringing petroleum oil into a heated zone maintained at a decomposingtemperature under such conditions as to form lighter products of unsaturated character, in combining the resulting' olefin products with chlorin and in reacting on the chlorinated body with an acetate.

6. The process of making derivatives of hydrocarbons which comprises passing petroleum oil with water through a heated zone maintained at a decomposing temperature under such conditions as to form lighter products of unsaturated character, in combining the resulting olefin products, with chlorin and in reacting on the chlorinated body with an alkali metal salt of an organic acid.

7. The process of making derivatives of hydrocarbons which comprises passing petroleum oil with water through a heated tube maintained at a decomposing temperature under such conditions as to form lighter products of unsaturated character, in combining the resulting olefin products with chlorin and in reacting with the chlorinated body with an alkali metal salt of an organic acid.

8. The process of making derivatives of hydrocarbons which comprises passing petroleum oil with water through a heated zone maintained at a decomposing temperature under such conditions as to form lighter products of unsaturated character, in G011.- bining the resulting olefin products with chlorin, and in reacting with the chlorinated body with a salt of an organic acid.

9. The process of making derivatives of hydrocarbons which comprises passing petroleum oil through a heated zone maintained at a decomposing temperature under such conditions as to form light products of unsaturated character, in combining these unsaturated products with chlorin and in reacting on the chlorinated body with an. alkali metal salt of acetic acid.

10. The processof making derivatives of hydrocarbons which comprises cracking kerosene under such conditions as to form olefin material, in saturating said olefin material with chlorinto form chlorin compounds and in contacting said chlorin compounds with a reagent capable of replacing chlorin.

11. The process of making derivatives of hydrocarbons which comprises passing a petroleum oil into aheated zonemaintained at a decol'nposing temperature under such conditions as to form lighterproducts of an unsaturated character, in chlorinating these unsaturated products and in subsequently replacing the chlorin by another element or radical.

12. The process of making derivatives of hydrocarbons which comprises cracklng kerosene under such conditions as to form olefin material having an iodin number exceeding 30'. in chlor nating sald olefin material toform chlorin compounds and in hydrocarbons which comprises cracking a petroleum oil under such conditions as to form lighter products of an unsaturated character, in chlorinating these unsaturated products and in subsequently replacing the chlorin by a substituent. a

14. The process of making derivatives of hydrocarbons which com olefin material, in chlorinating said olefin in contacting said dichlor material to form dichlor compounds and compounds with a reagent capable of replacing chlorin.

15. The hydrocarbons which comprises cracking a petroleum oil in a heated-zone under such conditions as'to form lighter products of an unsaturated character, in chlorinatin" these unsaturated. products with free chlorin and in subsequently replacing the chlorin.

16. The process of making derivatives of hydrocarbons which comprises passing petroleum oil through a heated zone at a temperature between 425", and 480 C. under such conditions as to form o'lefin material and in chlorinating said olefin material;

17. The process of making derivatives of hydrocarbons which comprises cracking petroleum to form olefin material, in treating said olefin material under such conditions as to form chlorin compounds and in contacting said chlorin compounds with a reagent capable of replacing chlorin.

18. The process-of making derivatives of hydrocarbons which comprises passing a petroleum oil into a heated zone maintained ata decomposing temperature under such conditions as to form lighter products of an unsaturated character having an iodin number above 30; in chlorinating these unsaturated products and in subsequently replacing the chlorin. a

' 19. The process of making derivatives of hydrocarbons-which comprises cracking an prises cracking- Qing kerosene under such condltlons as to form process of makingderivatives of having an iodin oil under such conditions as to produce light volatile hydrocarbons of an unsaturated character having'an iodin number'-in excess of 30, in exposing said products to the action of chlorin in the cold whereby chlorin isabsorbed with the evolution of heat forma more or less non-inflammable liquid and-in bringing said liquid into contact with a' reagent capable of replacing chlorin.

20. In the preparation of derivatives of hydrocarbons from unsaturated hydrocar bons the step which comprises treating cracked petroleum having an iodin number of more than 30 with chlorin and in subsequently contacting the product vwith a reexposing said products to the action of chlorin in the cold whereby chlorin is absorbed with the evolution of heat. forming a relatively non-inflammable liquid and in contacting said liquid with a reagent. capable of replacing chlorin. I V

23.. In the preparation of hydrocarbons from unsaturated gasolene material the step which comprises treating gasolene material number of more than 100 in subsequently contacting a reagent capable of replacwith chlorin and the product with ing chlorin.

' CARLETON ELLIS] 

